CN110230053A - A kind of method that laser melting coating prepares amorphous composite coating - Google Patents
A kind of method that laser melting coating prepares amorphous composite coating Download PDFInfo
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- CN110230053A CN110230053A CN201910588630.8A CN201910588630A CN110230053A CN 110230053 A CN110230053 A CN 110230053A CN 201910588630 A CN201910588630 A CN 201910588630A CN 110230053 A CN110230053 A CN 110230053A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 63
- 238000000576 coating method Methods 0.000 title claims abstract description 63
- 238000002844 melting Methods 0.000 title claims abstract description 25
- 230000008018 melting Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 54
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 36
- 238000005253 cladding Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention discloses a kind of method that laser melting coating prepares amorphous composite coating, belongs to the modified technical field of alloy surface coating.The method of the invention are as follows: titanium alloy is pre-processed, according to atomic ratio be (50~60): (15~25) by Zr powder, Al powder, Co powder: the ratio of (20~30) is uniformly mixed and is configured to cladding powder；Prepared powder and dehydrated alcohol are mixed, paste is modulated into and is bonded in titanium alloy substrate material surface, and in 300-350 DEG C of preheating 0.5-1h of vacuum, then in Ar, N2Or N2In-Ar mixed-gas environment, titanium alloy substrate surface is melted together with fore-put powder with laser melting coating, using high energy laser beam on titanium alloy prepares coating.The method of the invention prepares amorphous composite coating in titanium alloy surface, to improve the hardness and wearability of substrate material surface.
Description
Technical field
The present invention relates to a kind of methods that laser melting coating prepares amorphous composite coating, belong to the modified skill of alloy surface coating
Art field.
Background technique
The research of laser melting and coating technique has about 45 years history, although related theoretical and tentative research is very
It is more, but this technology is not widely used in actual industrial production, develops the relevant special metals of laser melting coating and gets over
More to attract attention.Amorphous alloy, also referred to as glassy metal.The metallic atom of amorphous alloy is in long-range in the arrangement of three-dimensional space
It is unordered, only keep a certain range of shortrange order.This unique crystal structure characteristic of amorphous alloy determines that it has
The unexistent excellent properties of many routine crystal alloy, such as higher hardness and strength and excellent wear-resisting and anti-rotten candle property
Energy.Based on these features, obtaining one layer of amorphous coating on traditional material surface by surface engineering technology can be improved its surface
Hardness, anti-corrosion and wear-resisting property, being modified field on the surface of the material has very huge potential using value, is now subjected to the country
The extensive attention of outer scholar is one of the hot spot of Current surface field of engineering technology research.By laser melting and coating technique and amorphous
The advantage of technology of preparing combines, and can satisfy requirement of the material surface to high-wearing feature and high corrosion resistance, while can fill
The tough sexual clorminance of basis material is waved in distribution, to improve the comprehensive performance and service life of material entirety.
It is obtained by the solution that has studied to Materialbearbeitung mit Laserlicht field related patents and paper, amorphous cladding coating will be at
For the new material of the wear-resisting area research of material surface and a kind of great development and application potentiality of application.But due to laser melting coating condition
Form coexists with crystal phase for lower amorphous phase and Forming Mechanism is not clear, the ingredient design and control, technological parameter of amorphous coating
Unstable, obtained properties of coating is not able to satisfy service condition complexity occasion.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that laser melting coating prepares amorphous composite coating, obtain high rigidity, height
Wearability and compact coating, specifically includes the following steps:
(1) pre-process to titanium alloy: polishing, cleaning are spare after dry；
(2) will be (50~60): (15~25) according to atomic ratio by Zr powder, Al powder, Co powder: (20~30), which are uniformly mixed, prepares
At cladding powder, Zr powder, Al powder, Co powder purity be not less than 99.95%.
(3) prepared powder and dehydrated alcohol are mixed, is modulated into paste and is bonded in titanium alloy substrate material surface, and
In 300-350 DEG C of preheating 0.5-1h of vacuum, then under protective atmosphere, with laser melting coating titanium alloy substrate surface and preset powder
End melt together, using high energy laser beam on titanium alloy prepares coating.
Preferably, step (1) of the present invention removes surface film oxide specifically includes the following steps: with sand paper polishing titanium alloy,
Titanium alloy after polishing is put into the NaOH aqueous solution that concentration is 4-6% and impregnates 5-10min, is then rinsed with water, and be put into nothing
With ultrasonic cleaning in water-ethanol, the greasy dirt and impurity of surface remaining are removed；After cleaning, done under 60-80 DEG C of vacuum environment
Dry 0.5-1h.
Preferably, in step (2) of the present invention ball milling parameter are as follows: rotational speed of ball-mill 45-60r/min, ratio of grinding media to material 15:1-
20:1, Ball-milling Time 2.5-3h, average particle size is 200-300 mesh after ball milling.
Preferably, the laser melting coating device that step (3) of the present invention uses is CO2Laser, laser power 3.5-4.0kW,
Spot diameter is 4mm, scanning speed 350-400mmmin-1。
Preferably, protective gas is Ar, N in step (3) of the present invention2Or N2- Ar mixed gas, flow velocity 18-30L
h-1。
Beneficial effect of the present invention and innovative point are as follows:
(1) macro morphology of material of the present invention is good, produces that dilution rate is low, the porosity is low and compact coating.
(2) content of amorphous is up to 55.8% in the zirconium-base amorphous coating of the present invention, and amorphous can be improved titanium alloy surface hardness
And wearability.
Detailed description of the invention
Fig. 1 is the SEM micrograph of coating made from embodiment 1；
Fig. 2 is the X ray diffracting spectrum of coating made from embodiment 1.
Specific embodiment
In order to deepen the understanding of the present invention, below with reference to embodiment, the invention will be further described, and the embodiment is only
It is used to explain the present invention, is not intended to limit the scope of the present invention.；Cladding material each component comes in the embodiment of the present invention
Source information is as shown in the table:
Embodiment 1
A method of amorphous composite coating being prepared in TC4 titanium alloy surface, specifically includes the following steps:
(1) with abrasive paper for metallograph polishing TC4 titanium alloy, surface film oxide is removed, the TC4 titanium alloy after polishing is put into quality percentage
10min is impregnated in the NaOH aqueous solution that concentration is 4%, is then rinsed and is put into dehydrated alcohol with clear water and be cleaned by ultrasonic, removal table
The greasy dirt and impurity of face remaining；After cleaning, in 60 DEG C of dry 1h；
(2) the Zr powder for being 99.99% using purity, Al powder, Co powder will be according to atomic ratio by Zr powder, Al powder, Co powder as raw material
50:25:25 mixing, is uniformly mixed obtained cladding powder for Zr powder, Al powder, Co powder by way of ball milling, and the parameter of ball milling is
Rotational speed of ball-mill 45r/min, ratio of grinding media to material 15:1, Ball-milling Time 3h.Average particle size is 200 mesh, TC4 titanium alloy substrate sizes after ball milling
For 60mm × 12mm × 4mm；
(3) 60mm × 4mm × 1mm drying strip initialization layer is made in cladding powder to be put on substrate, and 300 in vacuum drying oven
DEG C preheating 1h.Then in N2It protects in environment, through laser melting coating device TC4 titanium alloy substrate is melted together with initialization layer, passed through
Coating is formed on TC4 titanium alloy after high energy laser beam processing.The laser melting coating device used is CO2Laser, laser power are
3.5kW, spot diameter 4mm, scanning speed 350mmmin-1, N2Flow velocity is 18Lh-1。
The coating that step (3) obtains is processed into bulk using wire cutting machine, is aided with dioxygen resin and carries out edge sample, with not
Scanning electron microscope sample is made in the sand paper of one-size, and is corroded with wang aqueous solution, watches its scanning electron microscopic picture, microscopic structure shape
Looks are as shown in Figure 1, the defects of cladding layer flawless hole；Extension elongation occurs for cladding layer on matrix and clad layer surface, is formed
A very thin layer plane is brilliant；When cooling velocity, which reaches amorphous alloy, forms critical speed, there is large area without knot in the middle part of coating
The amorphous area of brilliant feature.Fig. 2 is the X ray diffracting spectrum on composite coating surface, it can be seen from the figure that being 30 ° -45 ° in 2 θ
In range, map shows the trend at obvious amorphous diffusing scattering peak, illustrates that composite coating has the tendency that amorphous phase formation；In addition,
Weaker Zr has been superimposed on diffusing scattering peak6Al2Co, crystal phase peak and AlZr2、AlTi2Phase.Show in cladding layer, produces
Partially crystallizable phase；Pseudo-Voigt function is carried out to cladding layer X ray diffracting spectrum and Verdon approximating method is analyzed and counted
It calculates, the volume content that can obtain amorphous phase in composite coating is 55.8%.
Embodiment 2
A method of amorphous composite coating being prepared in TC4 titanium alloy surface, specifically includes the following steps:
(1) with abrasive paper for metallograph polishing TC4 titanium alloy, surface film oxide is removed, the TC4 titanium alloy after polishing is put into quality percentage
8min is impregnated in the NaOH aqueous solution that concentration is 5%, is then rinsed and is put into dehydrated alcohol with clear water and be cleaned by ultrasonic, removal table
The greasy dirt and impurity of face remaining；After cleaning, in 70 DEG C of dry 0.7h；
(2) the Zr powder for being 99.99% using purity, Al powder, Co powder will be according to atomic ratio by Zr powder, Al powder, Co powder as raw material
55:23:22 mixing, is uniformly mixed obtained cladding powder for Zr powder, Al powder, Co powder by way of ball milling, and the parameter of ball milling is
Rotational speed of ball-mill 50r/min, ratio of grinding media to material 17:1, Ball-milling Time 3h.Average particle size is 250 mesh, TC4 titanium alloy substrate sizes after ball milling
For 60mm × 12mm × 4mm；
(3) 60mm × 4mm × 1mm drying strip initialization layer is made in cladding powder to be put on substrate, and 325 in vacuum drying oven
DEG C preheating 0.7h.Then in Ar protection environment, through laser melting coating device TC4 titanium alloy substrate is melted together with initialization layer, is led to
Coating is formed on TC4 titanium alloy after crossing high energy laser beam processing.The laser melting coating device used is CO2Laser, laser power
For 3.8kW, spot diameter 4mm, scanning speed 380mmmin-1, Ar flow velocity is 20Lh-1。
Embodiment 3
A method of amorphous composite coating being prepared in TC4 titanium alloy surface, specifically includes the following steps:
(1) with abrasive paper for metallograph polishing TC4 titanium alloy, surface film oxide is removed, the TC4 titanium alloy after polishing is put into quality percentage
5min is impregnated in the NaOH aqueous solution that concentration is 6%, is then rinsed and is put into dehydrated alcohol with clear water and be cleaned by ultrasonic, removal table
The greasy dirt and impurity of face remaining；After cleaning, in 80 DEG C of dry 0.5h；
(2) the Zr powder for being 99.99% using purity, Al powder, Co powder will be according to atomic ratio by Zr powder, Al powder, Co powder as raw material
58:20:22 mixing, is uniformly mixed obtained cladding powder for Zr powder, Al powder, Co powder by way of ball milling, and the parameter of ball milling is
Rotational speed of ball-mill 60r/min, ratio of grinding media to material 20:1, Ball-milling Time 3h.Average particle size is 300 mesh, TC4 titanium alloy substrate sizes after ball milling
For 60mm × 12mm × 4mm；
(3) 60mm × 4mm × 1mm drying strip initialization layer is made in cladding powder to be put on substrate, and 350 in vacuum drying oven
DEG C preheating 0.5h.Then in Nr2- Ar is protected in environment, and TC4 titanium alloy substrate is melted together with initialization layer through laser melting coating device
Change, forms coating on TC4 titanium alloy after processing by high energy laser beam.The laser melting coating device used is CO2Laser, laser
Power is 4kW, spot diameter 4mm, scanning speed 400mmmin-1, Nr2- Ar flow velocity is 30Lh-1。
The coating of embodiment 2 ~ 3 is tested using with the identical mode of embodiment 1, it can be seen that cladding layer pattern with
Extension elongation occurs for cladding layer on the defects of embodiment 1 is similar, flawless hole, matrix and clad layer surface, is formed very thin
One layer plane is brilliant；Pseudo-Voigt function is carried out to cladding layer X ray diffracting spectrum and Verdon approximating method is analyzed and counted
It calculates, it is 39.8% that the volume content that can obtain amorphous phase in composite coating in embodiment 2 and 3, which is respectively 47.6%,.
Claims (5)
1. a kind of method that laser melting coating prepares amorphous composite coating, which is characterized in that specifically includes the following steps:
(1) pre-process to titanium alloy: polishing, cleaning are spare after dry；
(2) be (50~60): (15~25) according to atomic ratio by Zr powder, Al powder, Co powder: (20~30), which are uniformly mixed, prepares
At cladding powder；
(3) prepared powder and dehydrated alcohol are mixed, is modulated into paste and is bonded in titanium alloy substrate material surface, and true
Empty 300-350 DEG C of preheating 0.5-1h, then under protective atmosphere, with laser melting coating titanium alloy substrate surface and fore-put powder one
Rise fusing, using high energy laser beam on titanium alloy prepares coating.
2. the method that laser melting coating prepares amorphous composite coating according to claim 1, it is characterised in that: step (1) is specific
The following steps are included: removing surface film oxide with sand paper polishing titanium alloy, it is 4-6%'s that the titanium alloy after polishing, which is put into concentration,
5-10min is impregnated in NaOH aqueous solution, is then rinsed with water, and is put into dehydrated alcohol with ultrasonic cleaning, removal surface remaining
Greasy dirt and impurity；After cleaning, the dry 0.5-1h under 60-80 DEG C of vacuum environment.
3. the method that laser melting coating prepares amorphous composite coating according to claim 1, it is characterised in that: ball in step (2)
The parameter of mill are as follows: rotational speed of ball-mill 45-60r/min, ratio of grinding media to material 15:1-20:1, Ball-milling Time 2.5-3h, average grain after ball milling
Degree is 200-300 mesh.
4. the method that laser melting coating prepares amorphous composite coating according to claim 1, it is characterised in that: step (3) uses
Laser melting coating device be CO2Laser, laser power 3.5-4.0kW, spot diameter 4mm, scanning speed 350-
400mm·min-1。
5. the method that laser melting coating prepares amorphous composite coating according to claim 1, it is characterised in that: protected in step (3)
Protecting atmosphere is Ar, N2Or N2- Ar mixed gas, flow velocity 18-30Lh-1。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139474A (en) * | 2020-03-10 | 2020-05-12 | 昆明理工大学 | Method for preparing amorphous composite coating by laser cladding |
| CN111850543A (en) * | 2020-06-22 | 2020-10-30 | 昆明理工大学 | Laser cladding seven-element high-entropy alloy coating and preparation method thereof |
| CN113351372A (en) * | 2021-06-07 | 2021-09-07 | 珠海格力电器股份有限公司 | Zr-based amorphous coating, preparation process thereof and application thereof in electric purification |
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| WO2015175167A1 (en) * | 2014-05-12 | 2015-11-19 | Siemens Energy, Inc. | Method of inducing porous structures in laser-deposited coatings |
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| CN109439995A (en) * | 2018-12-29 | 2019-03-08 | 宝钢轧辊科技有限责任公司 | High entropy amorphous alloy coating and preparation method thereof |
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2019
- 2019-07-02 CN CN201910588630.8A patent/CN110230053A/en active Pending
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| CN102703842A (en) * | 2012-06-15 | 2012-10-03 | 北京航空航天大学 | Zirconium base blocky amorphous/nanocrystalline alloy with antibacterial action and preparation method thereof |
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| CN111850543A (en) * | 2020-06-22 | 2020-10-30 | 昆明理工大学 | Laser cladding seven-element high-entropy alloy coating and preparation method thereof |
| CN113351372A (en) * | 2021-06-07 | 2021-09-07 | 珠海格力电器股份有限公司 | Zr-based amorphous coating, preparation process thereof and application thereof in electric purification |
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